U.S. patent application number 11/341622 was filed with the patent office on 2006-10-05 for polar monomer-olefin copolymer and process for producing the same.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. Invention is credited to Masayuki Fujita, Makoto Uemura.
Application Number | 20060223944 11/341622 |
Document ID | / |
Family ID | 36999092 |
Filed Date | 2006-10-05 |
United States Patent
Application |
20060223944 |
Kind Code |
A1 |
Uemura; Makoto ; et
al. |
October 5, 2006 |
Polar monomer-olefin copolymer and process for producing the
same
Abstract
A polar monomer-olefin copolymer comprising a polar monomer unit
in an amount of 50 to 75% by mol and an olefin unit in an amount of
25 to 50% by mol, and containing a chain structure consisting of
two or more olefin units; a process for producing said copolymer
comprising the step of radically copolymerizing 100 parts by mol of
an olefin with 1 to 100 parts by mol of a polar monomer; and a
process for producing said copolymer comprising the step of
radically copolymerizing an olefin having a concentration in a
polymerization reactor of 0.04 to 100 mol/liter with a polar
monomer having a concentration therein of 0.01 to 25 mol/liter.
Inventors: |
Uemura; Makoto;
(Ichihara-shi, JP) ; Fujita; Masayuki; (Chiba-shi,
JP) |
Correspondence
Address: |
FOLEY AND LARDNER LLP;SUITE 500
3000 K STREET NW
WASHINGTON
DC
20007
US
|
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED
|
Family ID: |
36999092 |
Appl. No.: |
11/341622 |
Filed: |
January 30, 2006 |
Current U.S.
Class: |
525/242 |
Current CPC
Class: |
C08F 2/00 20130101; C08F
210/02 20130101; C08F 210/02 20130101; C08F 220/18 20130101; C08F
2500/03 20130101; C08F 210/02 20130101; C08F 220/14 20130101 |
Class at
Publication: |
525/242 |
International
Class: |
C08F 297/02 20060101
C08F297/02 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2005 |
JP |
2005-101702 |
Claims
1. A polar monomer-olefin copolymer, which: comprises a polar
monomer unit in an amount of 50 to 75% by mol, and an olefin unit
in an amount of 25 to 50% by mol, the total amount of both units
being 100% by mol; and contains a chain structure consisting of two
or more olefin units.
2. The polar monomer-olefin copolymer according to claim 1, wherein
the polar monomer-olefin copolymer has no short-branched structure
derived from the olefin.
3. The polar monomer-olefin copolymer according to claim 1, wherein
the chain structure consisting of two or more olefin units is
contained in an amount of 4.0 to 50% by mol, the total amount of
the polar monomer unit and the olefin unit being 100% by mol.
4. The polar monomer-olefin copolymer according to claim 1, wherein
the olefin unit is an ethylene unit.
5. The polar monomer-olefin copolymer according to claim 1, wherein
the polar monomer unit is an acrylic ester unit.
6. A process for producing a polar monomer-olefin copolymer, which:
comprises a polar monomer unit in an amount of 50 to 75% by mol,
and an olefin unit in an amount of 25 to 50% by mol, the total
amount of both units being 100% by mol; and contains a chain
structure consisting of two or more olefin units; the process
comprising the step of radically copolymerizing 100 parts by mol of
an olefin with 1 to 100 parts by mol of a polar monomer.
7. The process for producing a polar monomer-olefin copolymer
according to claim 6, wherein the polar monomer-olefin copolymer
has no short-branched structure derived from the olefin.
8. The process for producing a polar monomer-olefin copolymer
according to claim 6, wherein the chain structure consisting of two
or more olefin units is contained in an amount of 4.0 to 50% by
mol, the total amount of the polar monomer unit and the olefin unit
being 100% by mol.
9. The process for producing a polar monomer-olefin copolymer
according to claim 6, wherein the olefin unit is an ethylene
unit.
10. The process for producing a polar monomer-olefin copolymer
according to claim 6, wherein the polar monomer unit is an acrylic
ester unit.
11. A process for producing a polar monomer-olefin copolymer,
which: comprises a polar monomer unit in an amount of 50 to 75% by
mol, and an olefin unit in an amount of 25 to 50% by mol, the total
amount of both units being 100% by mol; and contains a chain
structure consisting of two or more olefin units; the process
comprising the step of radically copolymerizing an olefin having a
concentration in a polymerization reactor of 0.04 to 100 mol/liter
with a polar monomer having a concentration therein of 0.01 to 25
mol/liter.
12. The process for producing a polar monomer-olefin copolymer
according to claim 11, wherein the polar monomer-olefin copolymer
has no short-branched structure derived from the olefin.
13. The process for producing a polar monomer-olefin copolymer
according to claim 11, wherein the chain structure consisting of
two or more olefin units is contained in an amount of 4.0 to 50% by
mol, the total amount of the polar monomer unit and the olefin unit
being 100% by mol.
14. The process for producing a polar monomer-olefin copolymer
according to claim 11, wherein the olefin unit is an ethylene
unit.
15. The process for producing a polar monomer-olefin copolymer
according to claim 11, wherein the polar monomer unit is an acrylic
ester unit.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a polar monomer-olefin
copolymer comprising a polar monomer unit and an olefin unit, and a
process for producing said copolymer.
BACKGROUND OF THE INVENTION
[0002] In these years, there have been developed various polar
monomer-olefin copolymers for various purposes, which copolymers
have characteristics of both polymers; namely, characteristics of a
polar monomer polymer represented by a methacrylic polymer such as
transparency and a weather resistance, and characteristics of an
olefin polymer such as a water resistance.
[0003] As a polar monomer-olefin copolymer, POLYMER PREPRINTS, vol.
45, pages 707-708 (2004) discloses a methyl acrylate-1-alkene
alternating copolymer containing a methyl acrylate unit and a
1-alkene unit in nearly the same molar amount as each other.
SUMMARY OF THE INVENTION
[0004] However, there is a problem in that the above-mentioned
methyl acrylate-1-alkene alternating copolymer does not completely
have characteristics of both polymers of a methyl acrylate polymer
and a 1-alkene polymer, and therefore, there has been required a
copolymer having more well-balanced characteristics thereof.
[0005] In view of the above-mentioned problem in the conventional
art, the present invention has an object to provide a polar
monomer-olefin copolymer having well-balanced characteristics of
both polymers of a polar monomer polymer and an olefin polymer, and
a process for producing said copolymer.
[0006] The present invention is a polar monomer-olefin copolymer,
which:
[0007] comprises a polar monomer unit in an amount of 50 to 75% by
mol, and an olefin unit in an amount of 25 to 50% by mol, the total
amount of both units being 100% by mol; and
[0008] contains a main chain structure consisting of two or more
olefin units.
[0009] Also, the present invention is a process for producing a
polar monomer-olefin copolymer, which:
[0010] comprises a polar monomer unit in an amount of 50 to 75% by
mol, and an olefin unit in an amount of 25 to 50% by mol, the total
amount of both units being 100% by mol; and
[0011] contains a main chain structure consisting of two or more
olefin units; the process comprising the step of radically
copolymerizing 100 parts by mol of an olefin with 1 to 100 parts by
mol of a polar monomer. This process is hereinafter referred to as
"process-1".
[0012] Further, the present invention is a process for producing a
polar monomer-olefin copolymer, which:
[0013] comprises a polar monomer unit in an amount of 50 to 75% by
mol, and an olefin unit in an amount of 25 to 50% by mol, the total
amount of both units being 100% by mol; and
[0014] contains a main chain structure consisting of two or more
olefin units;
[0015] the process comprising the step of radically copolymerizing
an olefin having an initial concentration in a polymerization
reactor of 0.04 to 100 mol/liter with a polar monomer having an
initial concentration therein of 0.01 to 25 mol/liter. This process
is hereinafter referred to as "process-2", and the above-mentioned
proess-1 and process-2 are collectively referred to as "process of
the present invention".
[0016] In the present invention, the terms "polar monomer unit" and
"olefin unit" mean a unit of a polymerized polar monomer and a unit
of a polymerized olefin, respectively. Accordingly, when a polar
monomer is, for example, methyl acrylate
(CH.sub.2.dbd.CHCOOCH.sub.3), a polar monomer unit is a divalent
monomer unit of --CH.sub.2--CH(COOCH.sub.3)--, and when an olefin
is, for example, ethylene (CH.sub.2.dbd.CH.sub.2), an olefin unit
is a divalent monomer unit of --CH.sub.2--CH.sub.2--.
DETAILED DESCRIPTION OF THE INVENTION
[0017] A polar monomer in the present invention means a cyclic or
chain organic compound having 3 to 20 carbon atoms, which contains
a carbon-to-carbon double bond (C.dbd.C) conjugating with a
carbonyl or cyano group. Said organic compound may contain one or
more substituent groups such as a carbonyl group other than the
above-mentioned carbonyl group, a cyanb group other than the
above-mentioned cyano group, an amino group, a hydroxyl group and a
halogeno group.
[0018] Examples of the polar monomer are acrylic acid, an acrylic
ester, methacrylic acid, a methacrylic ester, acrylamide,
methacrylamide, an N-alkylacrylamide, an N-alkylmethacrylamide, an
N,N-dialkylacrylamide, an N,N-dialkylmethacrylamide, acrylonitrile,
methacrylonitrile, acrolein, methacrolein, and methyl vinyl ketone;
and a combination of two or more thereof. Among them, preferred is
an acrylic ester.
[0019] Examples of the above-mentioned acrylic ester are an alkyl
acrylate such as methyl acrylate, ethyl acrylate, n-propyl
acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate,
sec-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate,
isopentyl acrylate, sec-pentyl acrylate, tert-pentyl acrylate,
neopentyl acrylate, cyclopentyl acrylate, n-hexyl acrylate,
cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate,
2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl
acrylate, isobornyl acrylate, dicyclopentyl acrylate, menthyl
acrylate, noradamantyl acrylate, and adamantly acrylate; an aryl
acrylate such as phenyl acrylate, and tolyl acrylate; benzyl
acrylate; 2-methoxyethyl acrylate; 3-methoxybutyl acrylate;
2-hydroxyethyl acrylate; 2-hydroxypropyl acrylate; stearyl
acrylate; glycidyl acrylate; 2-aminoethyl acrylate;
.gamma.-(acryloyloxypropyl) trimethoxysilane;
.gamma.-(acryloyloxypropyl) dimethoxymethylsilane; an adduct of
ethylene oxide to acrylic acid; trifluoromethylmethyl acrylate;
2-trifluoromethylethyl acrylate; 2-perfluoroethylethyl acrylate;
2-perfluoroethyl-2-perfluorobutylethyl acrylate; 2-perfluoroethyl
acrylate; perfluoromethyl acrylate; diperfluoromethylmethyl
acrylate; 2-perfluoromethyl-2-perfluoroethylmethyl acrylate;
2-perfluorohexylethyl acrylate; 2-perfluorodecylethyl acrylate; and
2-perfluorohexadecylethyl acrylate. Among them, preferred is an
alkyl acrylate, and more preferred is methyl acrylate.
[0020] Examples of the above-mentioned methacrylic ester are an
alkyl methacrylate such as methyl methacrylate, ethyl methacrylate,
n-propyl methacrylate, isopropyl methacrylate, n-butyl
methacrylate, isobutyl methacrylate, sec-butyl methacrylate,
tert-butyl methacrylate, n-pentyl methacrylate, isopentyl
methacrylate, sec-pentyl methacrylate, tert-pentyl methacrylate,
neopentyl methacrylate, cyclopentyl methacrylate, n-hexyl
methacrylate, cyclohexyl methacrylate, n-heptyl methacrylate,
n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl
methacrylate, decyl methacrylate, dodecyl methacrylate, isobornyl
methacrylate, dicyclopentyl methacrylate, menthyl methacrylate,
noradamantyl methacrylate, and adamantly methacrylate; an aryl
methacrylate such as phenyl methacrylate, and tolyl methacrylate;
benzyl methacrylate; 2-methoxyethyl methacrylate; 3-methoxybutyl
methacrylate; 2-hydroxyethyl methacrylate; 2-hydroxypropyl
methacrylate; stearyl methacrylate; glycidyl methacrylate;
2-aminoethyl methacrylate; .gamma.-(methacryloyloxypropyl)
trimethoxysilane; .gamma.-(methacryloyloxypropyl)
dimethoxymethylsilane; an adduct of ethylene oxide to methacrylic
acid; trifluoromethylmethyl methacrylate; 2-trifluoromethylethyl
methacrylate; 2-perfluoroethylethyl methacrylate;
2-perfluoroethyl-2-perfluorobutylethyl methacrylate;
2-perfluoroethyl methacrylate; perfluoromethyl methacrylate;
diperfluoromethylmethyl methacrylate;
2-perfluoromethyl-2-perfluoroethylmethyl methacrylate;
2-perfluorohexylethyl methacrylate; 2-perfluorodecylethyl
methacrylate; and 2-perfluorohexadecylethyl methacrylate; and a
combination of two or more thereof.
[0021] Examples of the above-mentioned N-alkylacrylamide are
N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, and
N-phenylacrylamide, and a combination of two or more thereof.
[0022] Examples of the above-mentioned N,N-dialkylacrylamide are
N,N-dimethylacrylamide, N,N-diethylacrylamide and
N,N-diphenylacrylamide, and a combination of two or more
thereof.
[0023] Examples of the above-mentioned N-alkylmethacrylamide are
N-methylmethacrylamide, N-ethylmethacrylamide,
N-phenylmethacrylamide, and N-isopropylmethacrylamide, and a
combination of two or more thereof.
[0024] Examples of the above-mentioned N,N-dialkylmethacrylamide
are N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide and
N,N-diphenylmethacrylamide, and a combination of two or more
thereof.
[0025] An olefin in the present invention means a C.sub.2 to
C.sub.20 cyclic or chain olefin containing a radically
polymerizable carbon-to-carbon double bond. The olefin may contain
(i) one or more substituent groups such as a carbonyl group, a
cyano group, an amino group, a hydroxyl group and a halogeno group,
or (ii) one or more bonds such as an ether bond, as long as the
carbon-to-carbon double bond contained in the olefin does not
conjugate with a functional group having .pi. electrons, or does
not make a direct linkage with a hetero atom such as an oxygen
atom, a nitrogen atom and a sulfur atom, such as a vinyl ether
linkage (CH.sub.2.dbd.CH--O--). The olefin may be a combination of
two or more kinds of olefins.
[0026] Examples of the olefin as a hydrocarbon compound are
ethylene; an .alpha.-olefin such as propylene, 1-butene, 1-pentene,
1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene,
4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
vinylcyclohexane, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene,
and 2,4,4-trimethyl-1-pentene; methylidenecyclohexane;
ethylidenecyclohexane; limonene; pinene; carene; and camphene.
[0027] Examples of the olefin as a carbonyl group-containing
compound are ally acetate, .beta.-vinyl-.gamma.-lactone, methyl
allyl ketone, allyl aldehyde (acrolein), allylamide,
N-acetylallylamide, and N-allylacetamide.
[0028] An example of the olefin as a cyano group-containing
compound is 3-propene-1-nitrile.
[0029] An example of the olefin as an amino group-containing
compound is allylamine.
[0030] Examples of the olefin as a hydroxyl group-containing
compound are ally alcohol and homoally alcohol.
[0031] An example of the olefin as a halogeno group-containing
compound is allyl chloride.
[0032] Examples of the olefin as an ether bond-containing compound
are methyl ally ether, phenyl ally ether, allyl glycidyl ether, and
limonene oxide.
[0033] Among olefins mentioned above, preferred is ethylene or an
.alpha.-olefin.
[0034] In the present invention, the above-mentioned respective
amounts of a polar monomer unit, an olefin unit, and a main chain
structure consisting of two or more olefin units are measured
according to a .sup.13C-nuclear magnetic resonance (.sup.13C-NMR)
analysis comprising the steps of:
[0035] (1) preparing a solution of a polar monomer-olefin copolymer
in chloroform-d having a concentration of 50 mg/mL;
[0036] (2) analyzing the solution at a temperature within a range
of 20 to 45.degree. C. with a .sup.13C-NMR apparatus having a trade
name, EXCULIBER/270 MHz, manufactured by JEOL. Ltd., thereby
obtaining a .sup.13C-NMR spectrum;
[0037] (3) identifying respective peaks in the .sup.13C-NMR
spectrum corresponding to the following chain structures (a) to
(e); [0038] (a) P-P-P, [0039] (b) O-P-P and P-P-O, [0040] (c)
O-P-O, [0041] (d) P-O-O and O-O-P, and [0042] (e) O-O-O, wherein
"P" means a polar monomer unit, and "O" means an olefin unit,
[0043] (4) measuring peak areas of the respective peaks;
[0044] (5) dividing the respective peak areas by the number of
carbon atoms assigned to the respective peaks, thereby obtaining
the respective peak areas per one carbon atom, Aa, Ab, Ac, Ad and
Ae, which correspond to the above-mentioned chain structures (a) to
(e), respectively;
[0045] (6) assigning the values Aa to Ae to the following formulas
[1] and [2], thereby obtaining an amount of an olefin unit and an
amount of a main chain structure consisting of two or more olefin
units; and [0046] amount of an olefin unit (% by mol) amount
.times. .times. of .times. .times. an .times. .times. olefin
.times. .times. unit .times. .times. ( % .times. .times. by .times.
.times. mol ) = ( Ab / 2 + Ac + Ad / 2 + Ae ) .times. 100 / ( Ac +
Ab + Aa + Ab / 2 + Ac + Ad / 2 + Ae ) , [ 1 ] ##EQU1## [0047] and
[0048] amount of a main chain structure consisting of two or more
olefin units (% by mol) amount .times. .times. of .times. .times. a
.times. .times. main .times. .times. chain .times. .times.
structure .times. .times. consisting .times. .times. of .times.
.times. two .times. .times. or .times. .times. more .times. .times.
olefin .times. .times. units .times. .times. ( % .times. .times. by
.times. .times. mol ) = ( Ad + Ae ) .times. 100 / ( Ac + Ab + Aa +
Ab / 2 + Ac + Ad ) [ 2 ] ##EQU2##
[0049] (7) obtaining an amount of a polar monomer unit from the
following formula [3], [0050] amount of a polar monomer unit (% by
mol) amount .times. .times. of .times. .times. a .times. .times.
polar .times. .times. monomer .times. .times. unit .times. .times.
( % .times. .times. by .times. .times. mol ) = 100 - amount .times.
.times. of .times. .times. an .times. .times. olefin .times.
.times. unit . [ 3 ] ##EQU3##
[0051] The following is an example of the above-mentioned
.sup.13C-NMR analysis, the steps (1) to (3), of a methyl
acrylate-ethylene copolymer:
[0052] (1) preparing a solution of a methyl acrylate-ethylene
copolymer in chloroform-d having a concentration of 50 mg/mL;
[0053] (2) analyzing the solution at 22.degree. C. with a
.sup.3C-NMR apparatus having a trade name, EXCULIBER/270 MHz,
manufactured by JEOL Ltd., thereby obtaining a .sup.13C-NMR
spectrum; and
[0054] (3) identifying the following respective peaks in the
.sup.13C-NMR spectrum, wherein "M" means a methyl acrylate unit and
"E" means an ethylene unit; [0055] (a) a peak at nearly 41.4 ppm
derived from the methine carbon atom bonding to the ester group
(--COOCH.sub.3), which corresponds to the chain structure, M-M-M,
[0056] (b) a peak at nearly 43.2 ppm derived from the methine
carbon atom bonding to the ester group (--COOCH.sub.3), which
corresponds to the chain structures, E-M-M and M-M-E, [0057] (c) a
peak at 45.2 ppm derived from the methine carbon atom bonding to
the ester group (--COOCH.sub.3), which corresponds to the chain
structure, E-M-E, [0058] (d) two peaks at nearly 27.0 ppm and
nearly 29.3 ppm derived from respective .beta.- and
.gamma.-position methylene carbon atoms for a methine carbon atom
bonding to the ester group (--COOCH.sub.3), which correspond to the
chain structures, M-E-E and E-E-M, and [0059] (e) no peak
identified, which corresponds to the chain structure, E-E-E, and
therefore, Ae is assumed to be zero.
[0060] Accordingly, the peak area, Ad, in this example is obtained
from the following formula [4]: Ad=(peak area derived from a
.beta.-position methylene carbon atom+peak area derived from a
.gamma.-position methylene carbon atom).times.2/(2.times.3)
[4].
[0061] A radical polymerization method in the present invention is
not particularly limited as long as said method relates to a
radical polymerization mechanism. Examples thereof are (1) a
free-radical polymerization method, (2) a living-radical
polymerization method with a reversible addition-fragmentation
chain transfer, (3) a living-radical polymerization method with a
stable radical, and (4) a living-radical polymerization method with
a transition metal compound.
[0062] Examples of an initiator used in the above-mentioned
free-radical polymerization method (1) are an azo initiator, a
peroxide initiator, a substituent group-containing ethane
initiator, a photopolymerization initiator, and an
electron-transfer initiator.
[0063] Examples of the above-mentioned azo initiator are
2-(carbamoylazo)isobutyronitrile,
1,1'-azobis(cyclohexane-1-carbonitrile), 4,4'-azobis(4-cyanovaleric
acid), 2,2'-azobisisobutyronitrile,
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
(2RS,2'RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl
2,2'-azobis(2-methylpropionate),
2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride,
2,2'-azobis[2-(2-imidazolin-2-yl)propane] disulfate dihydrate,
2,2'-azobis(2-methylpropionamidine) dihydrochloride,
2,2'-azobis{2-[N-(2-carboxylethyl)amidino]propane} n-hydrate,
2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}
dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane],
2,2'-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamid-
e}, 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide},
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],
2,2'-azobis(N-butyl-2-methylpropionamide),
2,2'-azobis(N-cyclohexyl-2-methylpropionamide),
2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], and
2,2'-azobis(2,4,4-trimethylpentane).
[0064] Examples of the above-mentioned peroxide initiator are
dibenzoyl peroxide, di-t-butyl hydroperoxide, peroxy pivalates,
dodecylbenzene peroxide, t-butylperacetate, acetyl peroxide, and
lauroyl peroxide.
[0065] Examples of an initiator used in the above-mentioned
living-radical polymerization method with a reversible
addition-fragmentation chain transfer (2) are those exemplified
above in the free-radical polymerization method (1), and dormant
species. Regarding the dormant species, there are two methods: (i)
one method comprising the steps of (i-1) preparing dormant species
outside of a polymerization reactor, and (i-2) feeding said dormant
species to a polymerization reactor, and (ii) another method
comprising the step of feeding to a polymerization reactor a
combination of the above-mentioned initiator in the free-radical
polymerization method (1) such as 2,2'-azobisisobutyronitrile with
a polymerization regulator such as a sulfur compound (for example,
thioester), an iodine compound (for example, iodoform and ethyl
2-iodoacetate), an organic tellurium compound, and an organic
antimony compound, thereby preparing dormant species in the
polymerization reactor. When the dormant species is unstable
species, the method (ii) is preferable because the method (ii) does
not need to prepare such unstable dormant species outside of a
polymerization reactor.
[0066] Examples of an initiator used in the above-mentioned
living-radical polymerization method with a stable radical (3) are
those exemplified above in the free-radical polymerization method
(1), and dormant species particularly derived from a stable
radical. Any of those initiators may be combined with an additive
such as a nitroxide compound (for example,
2,2,6,6-tetramethyl-1-piperidinyloxy), and a cobalt porphyrin
complex.
[0067] Examples of an initiator used in the above-mentioned
living-radical polymerization method with a transition metal
compound (4) are those exemplified above in the free-radical
polymerization method (1), and an initiator composed of a
transition metal compound and a transferable atom or atomic
group-containing compound.
[0068] An example of the above-mentioned initiator composed of a
transition metal compound and a transferable atom or atomic
group-containing compound is an initiator composed of a metal
complex (hereinafter referred to as "component (A)") of a metal
compound containing a metal selected from the group consisting of
metals belonging to Groups 8 to 12 in the periodic table (IUPAC
1985) and an organic halogen compound (hereinafter referred to as
"component (B)"). The component (A) may be a combination of two or
more kinds of said metal complexes.
[0069] The component (A) containing a ruthenium atom as a central
metal atom is preferably dichlorotris(triphenylphosphine)ruthenium,
dichlorotris(tributylphosphine)ruthenium,
dichloro(cyclooctadiene)ruthenium, dichloro(benzene)ruthenium,
dichloro-p-cymeneruthenium, dichloro(norbornadiene)ruthenium,
cis-dichlorobis(2,2'-bipyridine)ruthenium,
dichlorotris(1,10-phenanthrolin)ruthenium,
(carbonyl)chloro(hydrido)tris(triphenylphosphine)ruthenium,
chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium,
chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)
ruthenium, chloro(indenyl)bis(triphenylphosphine)ruthenium,
chloro(2-N,N-dimethylaminoindenyl)bis(triphenylphosphine)
ruthenium,
(ethylene)indenylbis(triphenylphosphine)ruthenium(pentafluoro
phenyl)borate, or (ethylene)indenylbis(triphenylphosphine)ruthenium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; or a combination of
two or more thereof. Among them, more preferred is
dichlorotris(triphenylphosphine)ruthenium,
chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)
ruthenium, chloro(indenyl)bis(triphenylphosphine)ruthenium,
chloro(2-N,N-dimethylaminoindenyl)bis(triphenylphosphine)
ruthenium,
(ethylene)indenylbis(triphenylphosphine)ruthenium(pentafluoro
phenyl)borate, or (ethylene)indenylbis(triphenylphosphine)ruthenium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and further
preferred is chloro (indenyl) bis (triphenylphosphine) ruthenium or
ethylene(indenyl)bis(triphenylphosphine)ruthenium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
[0070] The component (A) containing an iron atom as a central metal
atom is preferably a binuclear complex of an iron atom such as a
dicarbonyl(cyclopentadienyl)iron dimer and a
dicarbonyl(pentamethylcyclopentadienyl)irondimer;a ferrocene
compound such as ferrocene, acetylferrocene,
1,1'-bis(diphenylphosphino)ferrocene,
1,1'-bis(diisopropylphosphino)ferrocene,
bis(ethylcyclopentadienyl)iron,
bis(pentamethylcyclopentadienyl)iron,
bis(isopropylcyclopentadienyl)iron,
bis(tetramethylcyclopentadienyl)iron, n-butylferrocene,
tert-butylferrocene, .alpha.-(N,N-dimethylamino)ethylferrocene,
N,N-dimethylaminomethylferrocene, 1,1'-dimethylferrocene,
ethylferrocene, .alpha.-hydroxyethylferrocene,
hydroxymethylferrocene, and 1,1'-diacetylferrocene; iron(II)
acetate, iron(II) acetylacetonate, iron(II) bromide, iron(II)
chloride, iron(II) iodide, iron(III) bromide, iron(III) chloride,
(cyclohexadiene)irontricarbonyl;
(cyclooctatetraene)irontricarbonyl; iron(II) phthalocyanine,
dichlorobis(triphenylphosphine)iron;
bromo(dicarbonyl)(cyclopentadienyl)iron;
bromo(dicarbonyl)(pentamethylcyclopentadienyl)iron;
dicarbonyl(cyclopentadienyl)iodoiron;
dicarbonyl(pentamethylcyclopentadienyl)iodoiron; or a combination
of two or more thereof. Among them, preferred is a
dicarbonyl(cyclopentadienyl)iron dimer or a
dicarbonyl(pentamethylcyclopentadienyl)iron dimer.
[0071] An example of the component (A) containing a cobalt atom as
a central metal atom is cobaltocene.
[0072] An example of the component (A) containing a copper atom as
a central metal atom is a complex, whose ligand containing an atom
selected from the group consisting of atoms belonging to Groups 13
to 17 in the periodic table (IUPAC 1985) coordinates to the copper
atom.
[0073] Examples of the component (B) are a halogenated hydrocarbon
compound such as carbon tetrachloride, chloroform, dichloromethane,
monochloroethane, trichlorophenylmethane, dichlorodiphenylmethane,
monobromomethane, dibromomethane, tribromomethane, monoiodomethane,
diiodomethane, iodoform, 1-chlorobutane, 2-chlorobutane,
1-chloro-2-methylpropane, 1-bromobutane, 2-bromobutane,
1-bromo-2-methylpropane, 1-iodobutane, 2-iodobutane, and
1-iodo-2-methylpropane; an .alpha.-halogenocarbonyl compound such
as 2,2,2-trichloroacetone and 2,2-dichloroacetophenone; an
.alpha.-halogenocarboxylic ester such as ethyl 2-chloroacetate,
ethyl 2-bromoacetate, ethyl 2-iodoacetate, methyl 2-iodopropionate,
methyl 2,2,2-trichloroacetate, methyl 2,2-dichloroacetate, methyl
2-chloropropionate, ethyl 2-bromo-2-methylpropionate, ethyl
2-iodo-2-methylpropionate, ethyl 2-bromopropionate, ethyl
2-iodopropionate, dimethyl 2-chloro-2,4,4-trimethylglutarate,
dimethyl 2-iodo-2,4,4-trimethylglutarate,
1,2-bis(2'-bromo-2'-methylpropionyloxy)ethane,
1,2-bis(2'-iodo-2'-methylpropionyloxy)ethane,
1,2-bis(2'-bromopropionyloxy)ethane,
1,2-bis(2'-iodopropionyloxy)ethane,
2-(2'-bromo-2'-methylpropionyloxy)ethyl alcohol, and
2-(2'-iodo-2'-methylpropionyloxy)ethyl alcohol; and a
(1-halogenoalkyl)benzene derivative such as 1-bromo-1-phenylethane,
4-(1-bromoethyl)benzoic acid, and 4-(1-bromoethyl)benzoic ester;
and a combination of two or more thereof. Among them, preferred is
a halogenated hydrocarbon compound, an .alpha.-halogenocarbonyl
compound, or an .alpha.-halogenocarboxylic ester, and more
preferred is ethyl 2-bromo-2-methylpropionate, ethyl
2-iodopropionate, or 2-iodobutane.
[0074] A polar monomer-olefin copolymer of the present invention is
a random copolymer, which can be produced according to the
process-1 comprising the step of radically copolymerizing 100 parts
by mol of an olefin with 1 to 100 parts by mol, and preferably 25
to 2.5 parts by mol of a polar monomer from a viewpoint of
productivity of said copolymer, or according to the process-2
comprising the step of radically copolymerizing an olefin having a
concentration in a polymerization reactor of 0.04 to 100 mol/liter
with a polar monomer having a concentration therein of 0.01 to 25
mol/liter.
[0075] In the process-1, the amount of the olefin, "100 parts by
mol", and the amount of the polar monomer, "1 to 100 parts by mol",
mean the total amounts of respective monomers supplied to a
polymerization reactor throughout the entire polymerization,
respectively, and therefore, respective monomers are supplied to
the polymerization reactor in a lump at the beginning of
polymerization, or are supplied thereto continuously or
discontinuously in fractional amounts.
[0076] In the process-2, the concentration of the olefin, "0.04 to
100 mol/liter", and the concentration of the polar monomer, "0.01
to 25 mol/liter" mean their initial concentrations in the
polymerization reactor, respectively. Further olefin and/or further
polar monomer may be added to the polymerization reactor
continuously or discontinuously throughout the entire
polymerization, independently of the above-mentioned initial
concentrations.
[0077] When the amount of the polar monomer is not within the range
of 1 to 100 parts by mol per 100 parts by mol of the olefin in the
process-1, or when the initial concentration of the olefin is not
within the range of 0.04 to 100 mol/liter in the process-2, or the
initial concentration of the polar monomer is not within the range
of 0.01 to 25 mol/liter therein, there cannot be produced a polar
monomer-olefin copolymer, which comprises a polar monomer unit in
an amount of 50 to 75% by mol, and an olefin unit in an amount of
25 to 50% bymol, and contains a main chain structure consisting of
two or more olefin units, wherein the total amount of the polar
monomer unit and the olefin unit is 100% by mol. Particularly, when
the amount of the polar monomer is smaller than 1 part by mol per
100 parts by mol of the olefin in the process-1, or when the
concentration of the polar monomer is lower than 0.01 mol/liter in
the process-2, the copolymerization rate may be too slow, and when
the amount of the polar monomer is larger than 100 parts by mol per
100 parts by mol of the olefin in the process-1, or when the
concentration of the polar monomer is higher than 25 mol/liter in
the process-2, the olefin may not be copolymerized.
[0078] Feeding each of a polar monomer and an olefin in the amount
defined in the process of the present invention can produce a polar
monomer-olefin copolymer comprising a polar monomer unit in an
amount of 50 to 75% by mol and an olefin unit in an amount of 25 to
50% by mol, and containing a main chain structure consisting of two
or more olefin units, wherein the total amount of the polar monomer
unit and the olefin unit is 100% by mol. The process of the present
invention can produce a polar monomer-olefin copolymer comprising a
polar monomer unit in an amount of preferably 55 to 70% by mol and
an olefin unit in an amount of preferably 30 to 45% by mol, the
total amount of both units being 100% by mol, from a viewpoint of
(i) easy production of said copolymer and (ii) a good balance
between an amount of the olefin unit contained in said copolymer
and an amount of the main chain structure consisting of two or more
olefin units contained therein.
[0079] Feeding each of a polar monomer and an olefin in the amount
defined in the process of the present invention can control an
amount of a main chain structure consisting of two or more olefin
units contained in said copolymer. In order to produce a polar
monomer-olefin copolymer having an improved water resistance (one
of characteristics of an olefin polymer), the amount of a main
chain structure consisting of two or more olefin units is
preferably 4.0 to 50% by mol, more preferably 6.0 to 40% by mol,
and further preferably 10 to 30% by mol, wherein the total amount
of a polar monomer unit and an olefin unit is 100% by mol.
[0080] A .sup.13C-NMR analysis of a polar monomer-olefin copolymer
in the present invention with an equipment having an observation
frequency of nearly 67.5 MHz shows no existence of a short
chain-branched structure derived from the olefin, which usually
exists in a polyolefin produced according to a high-pressure
polymerization of an olefin, for example, a short chain-branched
structure such as an ethyl group or a butyl group derived from
ethylene, which usually exists in a low-density polyethylene
produced according to a high-pressure polymerization of
ethylene.
[0081] A molecular weight of a polar monomer-olefin copolymer in
the present invention can be controlled by changing an initial
concentration of respective monomers fed to a polymerization
reactor. For example, feeding methyl acrylate having an initial
concentration of 1 mol/liter or higher can produce a polar
monomer-olefin copolymer having a weight average molecular weight
of 10,000 or larger, which is a preferable weight average molecular
weight in view of processability of a copolymer produced.
[0082] Feeding each of a polar monomer and an olefin in the amount
defined in the process of the present invention can produce a polar
monomer-olefin copolymer having a molecular weight distribution of
preferably 1.0 to 5.0, and more preferably 1.0 to 2.5, which is
defined as a ratio of its weight average molecular weight (Mw) to
its number average molecular weight (Mn), Mw/Mn. Said molecular
weight distribution can be changed by devising a method such as a
method for adding a reagent (monomers, etc.) and a method for
controlling a polymerization temperature. There can be produced a
polar monomer-olefin copolymer having a molecular weight
distribution (Mw/Mn) of, for example, smaller than 1.6 by (1)
adding an additive in an amount of generally 1 to 50 mmol/liter,
the additive being mainly selected from a series of compounds used
for controlling living-radical polymerization, (2) adding monomers
in a relatively low concentration (usually, 1 to 4 mol/liter), and
(3) keeping a polymerization temperature and pressure and a
concentration of respective components in as small fluctuation as
possible. On the other hand, there can be produced a polar
monomer-olefin copolymer having a molecular weight distribution
(Mw/Mn) of, for example, larger than 3.0 by (1) adding monomers in
a relatively high concentration (usually, 8 mol/liter or higher),
and (2) changing a polymerization temperature and a concentration
of respective components during polymerization.
[0083] An initiator in the above-mentioned free-radical
polymerization method (1) is fed to a polymerization reactor in a
concentration (initial concentration) of generally 0.01 to 1,000
mmol/liter, and preferably 0.1 to 100 mmol/liter from a viewpoint
of productivity of a copolymer produced. When said concentration is
lower than 0.01 mmol/liter, a copolymerization rate may be too
slow, and when said concentration is higher than 1,000 mmol/liter,
there may occur too many undesirable side reactions such as a
termination reaction.
[0084] An initiator in the above-mentioned living-radical
polymerization method with a reversible addition-fragmentation
chain transfer (2) is fed to a polymerization reactor in a
concentration (initial concentration) of generally 0.01 to 100
mmol/liter, and preferably 0.1 to 40 mmol/liter from a viewpoint of
a molecular weight distribution of a copolymer produced. When said
concentration is lower than 0.01 mmol/liter, a copolymerization
rate may be too slow, and when said concentration is higher than
100 mmol/liter, there may occur too many undesirable side reactions
such as a termination reaction.
[0085] The above-mentioned polymerization regulator is fed to a
polymerization reactor in a concentration (initial concentration)
of generally 0.01 to 2,000 mmol/liter, and preferably 0.1 to 500
mmol/liter from a viewpoint of a balance between productivity of a
copolymer produced and polymerization controllability. When said
concentration is lower than 0.01 mmol/liter, it may be difficult to
produce a copolymer having a narrow molecular weight distribution,
and when said concentration is higher than 2,000 mmol/liter, a
copolymerization rate may be too slow.
[0086] An initiator in the above-mentioned living-radical
polymerization method with a stable radical (3) is fed to a
polymerization reactor in a concentration (initial concentration)
of generally 0.01 to 100 mmol/liter, and preferably 0.1 to 40
mmol/liter from a viewpoint of a balance between productivity of a
copolymer produced and polymerization controllability. The
above-mentioned additive optionally combined with said initiator is
fed to a polymerization reactor in a concentration (initial
concentration) of generally 0.01 to 2,000 mmol/liter, and
preferably 0.1 to 500 mmol/liter from a viewpoint of a balance
between productivity of a copolymer produced and polymerization
controllability. When said concentration of the initiator is lower
than 0.01 mmol/liter, a copolymerization rate may be too slow, and
when said concentration thereof is higher than 100 mmol/liter,
there may occur too many undesirable side reactions such as a
termination reaction. When said concentration of the additive is
lower than 0.01 mmol/liter, it may be difficult to produce a
copolymer having a narrow molecular weight distribution, and when
said concentration thereof is higher than 2,000 mmol/liter, a
copolymerization rate may be too slow.
[0087] The component (A) in the above-mentioned living-radical
polymerization method with a transition metal compound (4) is fed
to a polymerization reactor in a concentration (initial
concentration) of preferably 0.01 to 100 mmol/liter, and more
preferably 0.1 to 40 mmol/liter, from a viewpoint of a balance
between productivity of a copolymer produced and polymerization
controllability. The component (B) therein is fed to a
polymerization reactor in a concentration (initial concentration)
of preferably 0.1 to 100 mmol/liter, and more preferably 0.5 to 60
mmol/liter, from a viewpoint of a balance between productivity of a
copolymer produced and polymerization controllability. When said
concentration of the component (A) is lower than 0.01 mmol/liter,
it may be difficult to control a copolymerization rate, and when
said concentration thereof is higher than 100 mmol/liter, a
copolymerization rate may be too slow. When said concentration of
the component (B) is lower than 0.1 mmol/liter, productivity of a
copolymer may be low, and when said concentration thereof is higher
than 100 mmol/liter, a copolymer may have a low molecular
weight.
[0088] The component (A) may be combined with.an additive such as a
Lewis acid and an amine compound. Said additive is fed to a
polymerization reactor in a concentration (initial concentration)
of preferably 0.5 to 1,000 mmol/liter, and more preferably 1 to 60
mmol/liter.
[0089] The process of the present invention is carried out at a
copolymerization temperature of generally -30 to 300.degree. C.,
preferably 0 to 280.degree. C. and more preferably 20 to
250.degree. C. from a viewpoint of productivity of a copolymer and
easy production thereof. When said temperature is higher than
300.degree. C., a copolymer once produced may be decomposed easily.
Particularly preferable copolymerization temperature is room
temperature to about 60.degree. C., because the process of the
present invention can be carried out with a relatively convenient
apparatus.
[0090] A copolymerization pressure in the process of the present
invention is not particularly limited. When the olefin is ethylene,
the pressure is preferably atmospheric pressure to 40 MPa, more
preferably 2 to 20 MPa, and further preferably 4 to 10 MPa, from a
viewpoint of productivity of a copolymer and easy production
thereof. When said pressure is lower than atmospheric pressure, it
may be difficult to promote a copolymerization, and when said
pressure is higher than 40 MPa, it may be difficult to carry out
the process of the present invention with a generalized
apparatus.
[0091] A copolymerization time in the process of the present
invention is generally determined properly depending on conditions
such as a kind of a copolymer produced and a polymerization
reactor, and is usually 15 seconds to 40 hours.
[0092] A copolymerization system in the process of the present
invention is not particularly limited. Examples thereof are a
continuous copolymerization system and a batch-wise
copolymerization system.
[0093] A copolymerization method in the process of the present
invention is not particularly limited. Examples thereof are a
slurry copolymerization method, a solution copolymerization method,
and a gas-phase copolymerization method. An example of a solvent in
a copolymerization method using the solvent is an inert hydrocarbon
solvent such as propane, pentane, hexane, heptane and octane.
[0094] The process of the present invention may use a chain
transfer agent such as hydrogen in order to regulate a molecular
weight of a copolymer produced.
[0095] An example of a representative use of the polar
monomer-olefin copolymer in the present invention is a use as an
acrylic rubber having an improvement in its physical property such
as water resistance and low-temperature resistance.
EXAMPLE
[0096] The present invention is explained with reference to the
following Examples, which do not limit the scope of the present
invention.
Example 1
[0097] A stainless-steel 400 mL-autoclave was thoroughly dried, and
then purged with nitrogen gas. There were put in the autoclave with
a syringe at a room temperature and an atmospheric pressure 9 mL of
methyl acrylate (polar monomer) manufactured by Tokyo Kasei Kogyo
Co. Ltd., and 90 mL of purified toluene (polymerization solvent),
respectively, and then, 657 mg of 2,2'-azobisisobutylonitrile
(initiator) manufactured by Wako Pure Chemical Industries, Ltd. was
put therein. Further, ethylene gas (olefin) was put therein under
pressure up to 4.6 MPa. The mixture was heated up to 60.degree. C.,
and then, was copolymerized for 30 minutes, wherein the pressure in
the autoclave rose together with said heating up to 60.degree. C.,
and reached a final pressure of 7.4 MPa. After completion of the
copolymerization, remaining ethylene gas was purged, and then, the
solvent contained in the copolymerization reaction mixture was
distilled away under reduced pressure, thereby obtaining a
copolymer. The copolymer was dried for about 3 hours at a room
temperature, and 1.4 g of the dried copolymer was obtained.
[0098] The copolymer was analyzed, and was found to have (i) a
weight average molecular weight (Mw) of 25,800, and a number
average molecular weight (Mn) of 8,800, in terms of a weight
average molecular weight of a standard polystyrene and a number
average molecular weight thereof, (ii) a molecular weight
distribution shown by a single peak, and (iii) a single glass
transition temperature of -19.8.degree. C. The molecular weight
distribution (Mw/Mn) was calculated to be 25,800/8,800=2.9.
[0099] The copolymer was also analyzed according to the
above-mentioned .sup.13C-NMR analysis, and the following peaks were
identified in its .sup.13C-NMR spectrum, wherein "M" and "E" are a
methyl acrylate unit and an ethylene unit, respectively:
[0100] (a) a peak at nearly 41.4 ppm derived from the methine
carbon atom bonding to the ester group (--COOCH.sub.3), which
corresponds to the chain structure, M-M-M,
[0101] (b) a peak at nearly 43.2 ppm derived from the methine
carbon atom bonding to the ester group (--COOCH.sub.3), which
corresponds to the chain structures, E-M-M and M-M-E,
[0102] (c) a peak at 45.2 ppm derived from the methine carbon atom
bonding to the ester group (--COOCH.sub.3), which corresponds to
the chain structure, E-M-E,
[0103] (d) two peaks at nearly 27.0 ppm and 29.3 ppm derived from
the methylene carbon atom, which corresponds to the chain
structures, M-E-E and E-E-M, and
[0104] (e) no peak identified, which corresponds to the chain
structure, E-E-E.
[0105] Peak areas of the above-identified respective peaks were
measured, and the measured respective peak areas were converted
into the areas per one carbon atom, thereby obtaining converted
peak areas of Aa (300.00), Ab (483.21), Ac (215.72), Ad (190.29)
and Ae (0.00), which correspond to the above-mentioned chain
structures (a) to (e), respectively, wherein the reason for Ae
being 0.00 was that no peak was identified.
[0106] The above convertedpeak areas of Aa (300.00), Ab (483.21),
Ac (215.72), Ad (190.29) and Ae (0.00) were assigned to the
above-mentioned formulas [1] and [2], thereby obtaining an amount
of an ethylene unit of 36% by mol, and an amount of a chain
structure consisting of two or more ethylene units of 12% by mol,
the total amount of the ethylene unit and the methyl acrylate unit
being 100% by mol. The above-obtained amount of the ethylene unit
was assigned to the above-mentioned formula [3], thereby obtaining
an amount of a methyl acrylate unit of 64% by mol.
[0107] The above .sup.13C-NMR spectrum showed existence of an ester
group (--COOCH.sub.3 group) derived from methyl acrylate, but
showed no existence of a short chain-branched structure such as an
ethyl group and a butyl group derived from ethylene.
[0108] Based on the above, it was determined that the
above-obtained copolymer was a methyl acrylate-ethylene copolymer
containing 36% by mol of the ethylene unit, 64% by mol of the
methyl acrylate unit, and 12% by mol of the chain structure
consisting of two or more ethylene units.
[0109] Results are summarized in Table 1, wherein respective
amounts of "monomer used" and "initiator used" are converted into
those represented by "part by mol", "mol/liter" and
"mmol/liter".
[0110] The above-mentioned weight average molecular weight (Mw) and
number average molecular weight (Mn) were measured according to a
gel permeation chromatography (GPC) under the below-mentioned
conditions, wherein a calibration curve was prepared using standard
polystyrenes:
[0111] equipment of TYPE 150CV manufactured by Milipore Waters Co.,
Ltd.;
[0112] column of SHODEX M/S 80;
[0113] measurement temperature of 145.degree. C.;
[0114] solvent of o-dichlorobenzene; and
[0115] sample concentration of 5 mg/8 mL.
[0116] The above-mentioned glass transition temperature was
determined according to a differential scanning calorimetry (DSC)
with an equipment of DSC-VII manufactured by Perkin-Elmer under the
below-mentioned conditions:
[0117] heating from 20 to 200.degree. C. at a rate of 20.degree.
C./minute, and keeping at 200.degree. C. for 10 minutes; then,
[0118] cooling from 200 to -100.degree. C. at a rate of 20.degree.
C./minute, and keeping at -100.degree. C. for 10 minutes; and
then,
[0119] measuring under heating from -100 to 300.degree. C. at a
rate of 20.degree. C./minute.
Example 2
[0120] A stainless-steel 400 mL-autoclave was thoroughly dried, and
then purged with nitrogen gas. There were put in the autoclave with
a syringe at a room temperature and an atmospheric pressure 18 mL
of methyl acrylate (polar monomer) manufactured by Tokyo Kasei
Kogyo Co. Ltd., and 180 mL of purified toluene (polymerization
solvent), respectively. The mixture was heated up to 60.degree. C.,
and ethylene gas (olefin) was put therein under pressure up to 5.0
MPa. Further, 1.31 g of 2,2'-azobisisobutylonitrile (initiator)
manufactured by Wako Pure Chemical Industries, Ltd. was put
therein, and then, the mixture was copolymerized for 4 hours. After
completion of the copolymerization, remaining ethylene gas was
purged, and then, the solvent contained in the copolymerization
reaction mixture was distilled away under reduced pressure, thereby
obtaining a copolymer. The copolymer was dried for about 4 hours at
a room temperature, and 6.71 g of the dried copolymer was
obtained.
[0121] The copolymer was analyzed, and was found to have (i) a
weight average molecular weight (Mw) of 5,400, and a number average
molecular weight (Mn) of 2,400, in terms of a weight average
molecular weight of a standard polystyrene and a number average
molecular weight thereof, (ii) a molecular weight distribution
shown by a single peak, and (iii) a single glass transition
temperature of -23.5.degree. C. The molecular weight distribution
(Mw/Mn) was calculated to be 5,400/2,400=2.3.
[0122] The copolymer was also analyzed according to the
above-mentioned .sup.13C-NMR analysis, thereby obtaining converted
peak areas of Aa (497.66), Ab (414.27), Ac (88.01), Ad (91.31) and
Ae (0.00).
[0123] The above converted peak areas of Aa to Ae were assigned to
the above-mentioned formulas [1] and [2], thereby obtaining an
amount of an ethylene unit of 25% by mol, and an amount of a chain
structure consisting of two or more ethylene units of 6.8% by mol,
the total amount of the ethylene unit and the methyl acrylate unit
being 100% by mol. The above-obtained amount of the ethylene unit
was assigned to the above-mentioned formula [3], thereby obtaining
an amount of a methyl acrylate unit of 75% by mol.
[0124] The above .sup.13C-NMR spectrum showed existence of an ester
group (--COOCH.sub.3 group) derived from methyl acrylate, but
showed no existence of a short chain-branched structure such as an
ethyl group and a butyl group derived from ethylene.
[0125] Based on the above, it was determined that the
above-obtained copolymer was a methyl acrylate-ethylene copolymer
containing 25% by mol of the ethylene unit, 75% by mol of the
methyl acrylate unit, and 6.8% by mol of the chain structure
consisting of two or more ethylene units.
[0126] Results are summarized in Table 1.
Example 3
[0127] Example 1 was repeated except that (1) the ethylene gas
pressure of 4.6 MPa was changed to 4.7 MPa, thereby obtaining a
final pressure of 8.0 MPa, and (2) the copolymerization time of 30
minutes was changed to 1 hour, thereby obtaining 2.05 g of a dried
copolymer.
[0128] The copolymer was analyzed, and was found to have (i) a
weight average molecular weight (Mw) of 14,400, and a number
average molecular weight (Mn) of 7,500, in terms of a weight
average molecular weight of a standard polystyrene and a number
average molecular weight thereof, (ii) a molecular weight
distribution shown by a single peak, and (iii) a single glass
transition temperature of -19.7.degree. C. The molecular weight
distribution (Mw/Mn) was calculated to be 14,400/7,500=1.9.
[0129] The copolymer was also analyzed according to the
above-mentioned .sup.13C-NMR analysis, thereby obtaining converted
peak areas of Aa (287.61), Ab (486.25), Ac (176.02), Ad (191.24)
and Ae (0.00).
[0130] The above converted peak areas of Aa to Ae were assigned to
the above-mentioned formulas [1] and [2], thereby obtaining an
amount of an ethylene unit of 34% by mol, and an amount of a chain
structure consisting of two or more ethylene units of 13% by mol,
the total amount of the ethylene unit and the methyl acrylate unit
being 100% by mol. The above-obtained amount of the ethylene unit
was assigned to the above-mentioned formula [3], thereby obtaining
an amount of a methyl acrylate unit of 66% by mol.
[0131] The above .sup.13C-NMR spectrum showed existence of an ester
group (--COOCH.sub.3 group) derived from methyl acrylate, but
showed no existence of a short chain-branched structure such as an
ethyl group and a butyl group derived from ethylene.
[0132] Based on the above, it was determined that the
above-obtained copolymer was a methyl acrylate-ethylene copolymer
containing 34% by mol of the ethylene unit, 66% by mol of the
methyl acrylate unit, and 13% by mol of the chain structure
consisting of two or more ethylene units.
[0133] Results are summarized in Table 1.
Example 4
[0134] A stainless-steel 400 mL-autoclave was thoroughly dried, and
then purged with nitrogen gas. There were put in the autoclave with
a syringe at a room temperature and an atmospheric pressure 354 mg
of dicarbonylcyclopentadienyliron dimer (component (A))
manufactured by Aldrich, 18 ml of methyl acrylate (polar monomer)
manufactured by Tokyo Kasei Kogyo Co. Ltd., and 80 mL of purified
toluene (polymerization solvent), respectively, and then, ethylene
gas (olefin) was put therein under pressure up to 4.6 MPa, and
further, 0.5 mL of a toluene solution of methyl 2-iodopropionate
(component (B)) having a concentration of 1 mol/liter was put
therein. The mixture was heated up to 60.degree. C. over about 10
minutes, and then, was copolymerized for 15 minutes, wherein the
pressure in the autoclave rose along with said heating up to
60.degree. C., and reached a final pressure of 7.6 MPa. After
completion of the copolymerization, remaining ethylene gas was
purged, and then, the solvent contained in the copolymerization
reaction mixture was distilled away under reduced pressure, thereby
obtaining a copolymer. The copolymer was dried for about 3 hours at
a room temperature, and 3.73 g of the dried copolymer was
obtained.
[0135] The copolymer was analyzed, and was found to have (i) a
weight average molecular weight (Mw) of 13,600, and a number
average molecular weight (Mn) of 7,900, in terms of a weight
average molecular weight of a standard polystyrene and a number
average molecular weight thereof, (ii) a molecular weight
distribution shown by a single peak, and (iii) a single glass
transition temperature of -26.6.degree. C. The molecular weight
distribution (Mw/Mn) was calculated to be 13,600/7,900=1.7.
[0136] The copolymer was also analyzed according to the
above-mentioned .sup.13C-NMR analysis, thereby obtaining converted
peak areas of Aa (227.65), Ab (334.37), Ac (128.97), Ad (201.00)
and Ae (0.00).
[0137] The above converted peak areas of Aa to Ae were assigned to
the above-mentioned formulas [1] and [2], thereby obtaining an
amount of an ethylene unit of 34% by mol, and an amount of a chain
structure consisting of two or more ethylene units of 18% by mol,
the total amount of the ethylene unit and the methyl acrylate unit
being 100% by mol. The above-obtained amount of the ethylene unit
was assigned to the above-mentioned formula [3], thereby obtaining
an amount of a methyl acrylate unit of 66% by mol.
[0138] The above .sup.13C-NMR spectrum showed existence of an ester
group (--COOCH.sub.3 group) derived from methyl acrylate, but
showed no existence of a short chain-branched structure such as an
ethyl group and a butyl group derived from ethylene.
[0139] Based on the above, it was determined that the
above-obtained copolymer was a methyl acrylate-ethylene copolymer
containing 34% by mol of the ethylene unit, 66% by mol of the
methyl acrylate unit, and 18% by mol of the chain structure
consisting of two or more ethylene units.
[0140] Results are summarized in Table 1. TABLE-US-00001 TABLE 1
Example 1 2 3 4 Monomer used Ethylene in solution (part by mol) 100
100 100 100 Methyl acrylate (part by mol) 4 14 3 8 Ethylene in
solution (mol/liter) 25 7 29 26 Methyl acrylate (mol/liter) 1 1 1 2
Initiator used 2,2'-Azobisisobutylonitrile (mmol/liter) 20 20 20
Component (A) (mmol/liter) 20 Component (B) (mmol/liter) 20
Copolymerization Temperature (.degree. C.) 60 60 60 60 Time
(minutes) 30 240 60 15 Methyl acrylate-ethylene copolymer produced
Mw 25,800 5,400 14,400 13,600 Mn 8,800 2,400 7,500 7,900 Mw/Mn 2.9
2.3 1.9 1.7 Glass transition temperature (.degree. C.) -19.8 -23.5
-19.7 -26.6 Amount of a methyl acrylate unit (% by mol) 64 75 66 66
Amount of an ethylene unit (% by mol) 36 25 34 34 Amount of a chain
structure consisting of two 12 6.8 13 18 or more ethylene units (%
by mol)
* * * * *